Colouring of polyester fiberes



United States PatentOfice 3,043,647 COLOURING F POLYESTER FIBRES GeorgesKopp, Mont-Saint-Aignan, Ren Eugene Marcel Gangneux, Rouen, and AlfredMaxime Edouard Baron, Paris, France, assignors to Compagnie Francaisedes Matieres Colorantes, Paris, France, a French company No Drawing.Filed Jan. 3, 1958, Ser. No. 706,896

Claims priority, application France Jan. 5, 1957 4 Claims. (Cl. 8-41)The present invention concerns improvements in the colouring ofpolyester fibres.

It is known that it is possible to dye polyester fibres by means of theso-called plastosoluble dyestuffs, which are used for dyeing celluloseacetate fibres. These dyes can be applied either at ordinary pressure inthe presence of carriers, the most common of which are o-phenylphenoland the chlorinated derivatives of benzene, or under superatmosphericpressure and consequently in the absence of carriers and in a shortertime. The shades obtained are generally rather bright; in many cases,however, they 'lack fastness, especially to light, to wet tests and tosublimation.

It is further known that it is possible to dye polyester fibres, underthe conditions used for the so-called plastosoluble dyestuffs, by meansof mixtures of diazotisable bases and coupling compounds belonging tothe series of arylides of ,B-hydroxynaphthoic acid. The correspondingpigments are formed on the fibre by simultaneous diazotisation andcoupling. Provided that the choice of base and arylide and the relationbetween the amounts of these substances fixed on the fibre are correct,the colours obtained are capable of satisfying to a high degree therequirements so far as fastness to light and Wet tests are concerned.Although from the absolute point of View the resistance to sublimationis satisfactory, in numerous cases, however, variations in shades whichcan be considerable are observed at the time of preforming. In addition,this method of dyeing has the disadvantage of being lengthy since twosuccessive treatments of the fibre are necessary.

It has already been proposed to dye, by conventional processes, certaintextile fibres by means of very finely dispersed pigmental dyestuffslike those which are quite commonlyused for the coloration of viscose orcellulose acetate in bulk. In most cases, however, the tinctori-al yieldis low and, in addition, the shades obtained are not sufficiently fastto rubbing for this solution to be capable of being applied in practice.

We have now found that dyestuifs of the general formula:

in which R represents the residue of a benzene amine and phericpressure.

3,043,647 Patented July 10, 1962 X represents an alkyl group possess, athigh temperature, an excellent aflinity for polyester fibres.

By the expression polyester fibres we mean quite generally the fibresobtained by the poly-condensation of di-acids with di-alcohols, and inparticular those obtained by the poly-condensation of terephthalic acidwith ethylene glycol. Such fibres are on the market under the namesTerylene, Dacron and Tergal.

The dyestufis of the. above general Formula I can be applied to thesefibres at a high temperature by any of the processes already used forthe coloration of the latter by means of other pigments. Dyeing can becarried out, for example, under superatmospheric pressure andattemperatures above 0., preferably at temperatures be-' tween 101 C. andC., by means of aqueous dispersions of the dyestufis of generalFormula 1. Another process comprises foularding the fibres by means ofaque ous dispersions of these dyestuffs and then subjecting them to atreatment at high temperature, preferably between 150 C. and 200 C.Also, after foularding bymeans of these aqueous dispersions, theimpregnated fibres can be subjected to steaming under super-atmos-Fabrics basedon polyester fibres can also be printed by means of pastescontaining aqueous dispersions of the said dyestuffs and then theprinted fibres subjected to'steaming under superatmospheric pressure.

Alkylarylsulphonat es and the products resulting from the condensationof sulphon-ated aromatic derivatives with aldehydes, such as themethylene-dinaphthylsulphonates, are particularly valuable auxiliarysubstances since they allow the preparation of a good dispersion of thedyestuflis and facilitate the taking up of the latter on the polyesterfibres. On the other hand, carriers, such as monoor poly-chlorinatedderivatives of the benzene series or diphenyl, can be added to the dyebath or to the printing pastes. These substances exert a swelling actionon the polyester fibres and are capable of improving the tinctorialyield. 'Inaddition, it is useful, and particularly so in.

be remedied which in all probability is due to the accumulation ofelectrical charges as a result of the circulation of the bath aroundhydrophobic fibres.

The dyestuffs of general Formula I give, with excellent yields, brightshades characterised by very good fastness. These shades are not ingeneral comparable with those obtained on cotton or obtained bycoloration of viscose in bulk. *It is necessary to consider that thefact of operating at high temperature has the efiect of giving to thepigment its definitive physical form, a result which is certainly notattained when the pigment is formed on the polyester fibre bydiazotisation and coupling.

The invention will be more clearly understood by reference to thefollowing examples which are purely illustrative.

Example 1 3.5 parts of "monochlorotoluene are emulsified in 10 parts ofwater by means of about 1.5 parts of the butyl ester of sulphonatedricinoleic acid. This emulsion is stufiof the following formula:

QN N

(previously dispersed with 2 parts of the sodium salt ofmethylene-dinaphthylsulphonic acid) is mixed therewith. 100 parts ofpolyester fibres, previously degreased by treatmentin alkaline medium inthe hot, areintroduced. The dyeing is carried out in an apparatus whichenables it to be effected under slight superatrnospheric pressure, whilethe temperature is kept at 105 C. for an hour. The treatment is finishedby subjecting the fibres to cleaning by ,alkaline reduction in a bathcontaining one to two grams .per litre of an alkylphenol-ethylene oxidecondensate.

The polyester fibres are dyed a bright orange shade, which is fast tolight, to wet tests, rubbing and sublimation.

' Example 2 3.5 parts of orthodichlorobenzene are emulsified in parts ofwater by means of about 1.5 parts of the butyl ester of sulphonate'drici-noleic acid. This emulsion is poured into 1000 parts of tepid waterand one part of the dyestuif of the formula: I

o c'in (previously dispersed by means 'of'2 partsoi the sodium salt ofmethylene-dinaphthylsulphon-ic acid). is mixed therewith. 100 parts ofamixed material made up ofpolyester/wool 'fibres, previously degreased inthe hot in a bath containing 21 to 2 g. per litre of analkylphenol-ethylene oxide condensate, are introduced. Dyeing iseffected under superatmospherio pressure while keeping the temperatureat 105 C. for one hour.

The polyester fibres are dyed a bluish-red shade, fast .to light, wettests, rubbing and sublimation, while the wool is only very slightlycoloured. This light shade is not of such nature that it diminshes thequality of the acid dyestufi which must be applied simultaneously orsubsequently to the wool; moreover, it readily disappears if the dyeingis followed by a slightly reducing cleaning treatment by means of a bathcontaining 1 to 2 g. per litre of an alkylphenol-ethylene oxidecondensate.

Example 3 and On dyeing under the same conditions, a scarlet colour ofgood brilliancy is obtained which possesses excellent fastness, whilethe wool is sufficiently unaffected to allow it to be easily dyedzover.

(was

Example 4 A printing paste is prepared comprising the followingconstituents Parts 'dyest'uft'of'the formula:

dyestufi of the formula:

sodium methylene-dinaphthylsulphona te l O CzHs monoethyl glycol Water300 1:2-aqueous solution of sodium chlorate (containing 1 part ofchlorate to 2 parts of water 30 thickener I the frame or roller process.There then follows a steaming process under superatmc spheric pressureat 120-130 C., for the purposes of fixing the dye, and finallythere is Abluish .red shade is obtained which has the same qualities of fastnessas those obtained in Example 2.

Example 7 an alkaline reducing treatment in the hot in a bath con- 5 Onreplacing the dyestuif used in Example 5 by the taining l to 2 g. perlitre of an alkylphenol-ethylene oxide mixture of dyestuffs used inExample 3, a scarlet colour condensate. possessing good fastness isobtained.

On the polyester fabric there is obtained a bluish red E l 8 shade whichhas the fastness characteristic of the dyes 7 8 obtained by theprocesses of the preceding examples. 10 On replacing the dyestuff usedin Example 6 by the Example 5 mixture of dyestuifs used in Example 4, abluish red A fabric which has been previously desized is shadepossessing excellent fastness 1s obtamed. foularded att a-bQFEhSOJ Cali?af tslrllspfensiolri containing 6 Example 9 ams'er reo e es 0 eorm a: grp 1 y 6 parts of a condensation product of oleyl alcohol with OH Oethylene oxide is dissolved in 881 parts of water at 30'--35 l l C. andinto this are introduced 100 parts of previously N=N 0 05115 degreasedpolyester fibre yarn on a bobbin.

The bath is circulated for some minutes and the fluid ()1 paste preparedwith the following constituents is poured Parts dyestuII of formula:

IIIOZ 0H C0-NH N=N horns 0.5

dyestuff of formula:

orr CO-NH ONZN- v born 0.5

sodium methylene-dinaphthylsulphouate 2 mixture of water and denaturedethyl alcohol 10 Example 6 A Tergal fabric, previously desized, isfoularded at about 50 C. in a bath containing 6 grams per litre of thedyestufi of the formula: I

(previously dispersed by means of twice its weight of sodiummethylene-dinaphthylsulphonate) and 50 grams per litre of a condensationproduct of ethylene oxide with stearic acid. The fabric thus foulardedis subjected to steaming for minutes under 1.8 to 2 kg. pressure andwashed for 5 minutes at the boil in an alkaline reducing bath containinga non-ionic detergent.

The fabric thus foularded is passed on a evenly dyed.

The temperature is raised to 125 130 C. and kept at this for an hour.The polyester fibres are dyed a bright orange shade endowed with goodgeneral fastness; the bobbin having been completely penetrated, thefibre is v Example 10 The dyestuffs used in Example 9 are replaced by amixture of the dyestuft of formula:

OH CO-NH 2 parts, previously dispersed, and of the dyestuif of formula:1

2 parts, previously dispersed.

The polyester fibre is dyed a dark navy blue shade endowed with goodgeneral fastness, more particularly to sublimation.

Example 11 A dye bath is prepared with 881 parts of water at 30- 35 C.and 6 parts of cetyl-trimethyl ammonium bro mide, and parts of polyesterfibre yarn are'introduced in the form of a crossed 'bobbin, previouslydegreased.

ace-ape? 4 The bathis circulated for. some minutes and a paste ,obtainedby mixing the following components is added:

operating in accordance with the process of Example 4.

After printing, steaming and alkaline reducing treatment Parts dyestufioi the formula:

sodium methylene-naphthylsulphonate ot-s mixture of water anddenaturedalcohol- 2 The dyeing is eifected as in Example the polyesterfiber is coloured a bluish red of great brilliance possessing goodgeneral fastness;

Example 12 p I On replacing the two dyestuffs used in Example 11 by thesame quantities of the following dyestufis, previously dispersed:

a very bright reddish violetpossessing good general fastnessisobtainedron polyester fibre.

Example 13 p A printing paste is prepared with the following'dyestu'fis:

under the same conditions, a red brown shade, having good generalfastness, is obtained on polyester fabric.

We claim:

1. Process for the colouration of polyethylene terephthalate textilematerial which comprises printing a fabn'c made from the fibres with aprinting paste containing an aqueous dispersion of a dyestuif on thegeneral formula.

in which R represents a phenyl radical substituted by at least onemember selected from the group consisting of hydrogen, halogen, .alkoxy,:nitro, cyano, phenyl amino,

:alkoxyphenylamino, land benzene azo group, and X represents analkylgroup, and subjecting the treated fibres to steaming undersuperatmospheric pressure at a temperature betweenlQl" C. and C.

2. .Process,,:for the coloration ,of polyethyleneterephthalate textilematerial which comprises dyeing the fibres under super atmosphericpressure and at a temperature Parts 0H co-Nrr-G-m C1 I vNEH 9 about 100C. with an aqueous dispersion of a dyestufi of the general formula:

in which R represents a phenyl radical substituted by at 10 least onemember selected from the. group consisting of hydrogen, halogen, alkoxy,nitro, cyano, phenyl amino, alkoxy phenyl amino, and benzene azo groupand X represents an alkyl group.

3. Process as claimed in claim 2 in which the temperature is between 101C. and 150 C.

4. Process for the coloration of polyethylene terephthalate textilematerial which comprises foularding the fibres with an aqueousdispersion of a dyestufi of the general formula:

OH (JO-NEG 10 in which R represents a phenyl radical substituted by atleast one member selected from the group consisting of hydrogen,halogen, alkoxy, nitro, cyano, phenyl amino, alkoxy phenyl amino, andbenzene azo group and X rep resents an alkyl group and subjecting thetreated fibres to a temperature between 150 C. and 200 C.

References Cited in the file of this patent UNITED STATES PATENTS OTHERREFERENCES J.S.D.C., Waters, December 1950, pp. 609-613.

Amer. Dyestufi Reporter, Zimmerman et 211., Apr. 25, 1955, pagesP296-P30 2.

Man-Made Textiles, March 1956, pp. 72 and 74.

Du Pont Bulletin D-73, February 1956, pages 3-13,

Wilmington, Del.

1. PROCESS FOR THE COLOURATION OF POLYETHYLENE TEREPHTHALATE TEXTILEMATERIAL WHICH COMPRISES PRINTING A FABRIC MADE FROM THE FIBRES WITH APRINTING PASTE CONTAINING AN AQUEOUS DISPERSION OF A DYESTUFF ON THEGENERAL FORMULA: